CN108602727A - 积层制造3d打印物品的方法 - Google Patents

积层制造3d打印物品的方法 Download PDF

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Publication number
CN108602727A
CN108602727A CN201680069612.3A CN201680069612A CN108602727A CN 108602727 A CN108602727 A CN 108602727A CN 201680069612 A CN201680069612 A CN 201680069612A CN 108602727 A CN108602727 A CN 108602727A
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printing
slurry
oil
nipaam
glue
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CN108602727B (zh
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王志光
何美泠
潘力诚
傅尹志
陈崇桓
张瑞根
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Kaohsiung Medical University
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Kaohsiung Medical University
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Abstract

一种积层制造3D打印物品的方法，包含（a）以3D打印机打印沉积一或多层浆体，其中浆体包含一陶瓷粉末的组合物；（b）进一步注入油于一或多层浆体周围，其中注入的油的高度低于浆体的高度；（c）重复步骤（a）和（b）直到得到一具有所需几何形状的本体；及（d）藉由加热烧结本体以得到3D打印物品，其中3D打印机的打印载座温度为30至80℃。

Description

积层制造3D打印物品的方法 技术领域
本发明是关于一种积层制造3D打印物品的方法。
背景技术
原料是3D打印的核心技术之一，目前塑料、金属、陶瓷是3大主流，不过放眼未来，多元材料的打印将成必然。
相对于塑料的早期运用，金属则是在3D打印发展较后期才出现，早期仍以塑料为主原料的时代，3D打印不被视为机器制造的技术，直到金属打印技术被开发出来，此一看法才逐渐扭转。目前金属3D打印主要有两种方法，一种是先将金属粉末铺平(或涂敷热敏塑料黏合剂)，直接用激光使之选择性地烧熔或黏合，后者黏合成形后再于热炉中烧结，另一种则是通过打印喷头挤出熔化金属，依照设计档移动喷射头，使喷出的金属精准成形。过去消费性3D打印机只能使用塑料材质，不过随着打印机与原料技术的进步，目前已有部分消费用机台可使用特殊材质的原料，像是将金属粉末与凝胶混合，至于纯金属的3D打印机，目前的价格仍然偏高，并不属于消费端层次。
除了塑料与金属外，陶瓷与玻璃也是3D打印原料之一，不过这两种原料的应用都有其局限，陶瓷打印目前常见约有两种方式，一种是陶瓷粉末是以打印头喷洒加入加凝结剂或加光硬化树脂的方式，另一种则是打印头挤出泥条，形成粗胚后再进炉烧制，不管是那一种方式，陶瓷打印都需要2阶段以上的制程，打印后再施釉窑烧，而且容易有变形、坯体干燥时间长及膨胀系数控制的问题。目前陶瓷打印的 最主要应用之一是在医疗领域，用以制作如假牙、骨骼等人体部位，陶瓷打印在此处的应用是先以断层扫描出齿模或骨骼形状，再以3D打印出陶瓷植入物，以期降低制作成本、加速愈合时间、达到客制化产品或缩小手术时间等困扰。
虽然市场上已有一些多孔性磷酸盐生物陶瓷植入物，但是机械性大多不好，且不易开发精密与复杂形状的骨材，导致开发成本太高，无进一步促进骨愈合治疗功能。本发明已利用新式的负温感水胶均压收缩技术开发多孔性双相磷酸盐(HAp/TCP)生物陶瓷制程，不仅具有微孔洞且可达较佳的机械应力，经成分与烧结条件控制亦可能不同双相磷酸盐(HAp/TCP)比例的生物陶瓷。若配合现今3D生物打印技术预期可客制化精密与复杂形状的多孔性骨材。进一步，可携带促进骨生长的药物，预计其能成为兼具骨引导与骨传导作用的前瞻性骨材。
早在1980年代就已经出现了，当时称作“积层制造”或“快速成型”，其应用在工业上大量制造前开模设计校正之用。直到近年这些技术专利陆续到期，加上工业发展基础的进步，将此技术渐渐普遍应用在生活上。此技术发展让过往再设计独特或客制化需求不再限制于成本上的问题，转而通过此项技术让可以简单呈现，大大降低时间跟成本之间的限制，让客制化这名词连带成为热门发展方向。由平面的二维结构转化为三维立体呈现。目前就发明人所知，除发明人已具有以负温感水胶均压收缩系统(p(NiPPAm)、p(NiPAAm-MMA)等等)来制作多孔陶瓷的专利与文献。其他尚无类似文献。此外，本发明是 以发展可3D打印的陶瓷材料打印技术，即利用负温感水胶均压收缩系统来打印标准化与客制化陶瓷成品，并且利用疏水性液油控温与协助陶瓷烧结过程有更好收缩致密化功能。可应用在传统陶瓷、生医陶瓷、电子与结构性陶瓷等等市场价值均具有高的潜力。
发明内容
本发明3D陶瓷打印专利主要是以负温感水胶可均压收缩的模板来简化制程，并可获得良好双连续相的互穿性孔洞通道、良好控制的收缩率，此外高致密化使得陶瓷支架机械性甚佳等好处是本发明可以有机会得到专利技术的方向。相对应的3D打印材料系统，唯独陶瓷材料尚在研究开发的初始阶段。虽然同样类型技术已有数种，然而本技术具高特异性与高致密烧结的特性，在传统陶瓷、玻璃、精密陶瓷与金属等等市场价值均具有高的潜力。此外，尤其在医疗器材的植入性生物陶瓷植体与牙科用氧化锆、氧化铝等牙冠陶瓷材料等更是好的目标。
例如：可应用在人工生物陶瓷植体的标准化与客制化制程。无论如何多孔性生物陶瓷的孔隙率与尺寸控制/要利于骨细胞生长与药物控制范围，多孔质可吸收性生物陶瓷制作方法/多孔性陶瓷制作技术虽然已广为生医业界应用，然而其应用的发泡技术或以高分子粒残留法达成时，往往应用的材料种类并不一定能用在磷酸钙生物陶瓷的多孔性制作上，原因是材料是否有适当的机械性与无毒性，再者要达到双连续相的互有联通的通道孔洞也是另一种要解决的问题。
本发明的目的是将具负温感性水胶/陶瓷材料，通过3D打印技术 (积层制造)成型技术制作成型。方法是利用负温感性水胶系统(p(NiPAAm)、p(NiPAAm-MMA)等等)的逆温感特性与生物陶瓷粉末搅拌使用，再通过3D打印设备制作成型。负温感性水胶溶液根据陶瓷粉末的不同，调整其黏度、浓度及添加比例。负温感性水胶溶液可控制温度来有效提高陶瓷粉末间均匀收缩，可取代大多陶瓷制作上需通过机械力挤压定型的成本与时间。因负温感性水胶特性，摆脱模具限制，提升其成型方式与样式的多元，跟进3D打印技术发展脚步，利用负温感性水胶逆温感特性，控制温度打印成型，使其型态上可不具限制，且具有规则性的互穿孔洞，突破传统生物陶瓷制作上的限制。
因此，本发明提供一具负温感性可均压收缩水胶混合陶瓷粉末系统可进行3D打印陶瓷结构，其包含负温感性水胶使用，所述负温感性水胶可为例如：N-异丙基丙烯酰胺聚合物(poly(N-isopropylacrylamide；p(NiPAAm))、N-异丙基丙烯酰胺-甲基丙烯酸共聚合物(poly(N-isopropylacrylamide-co-methacrylic acid；p(NiPAAm-MAA))及类似负温感化合物；所述生物陶瓷材料可为氢氧基磷灰石(HA)、磷酸三钙(TCP)、高密度氧化铝(Al2O3)、氧化锆(ZrO2)、生物活性玻璃(Biogiass；BG)及类似生物陶瓷材料；所述3D打印生物陶瓷打印技术可为沉积成型(FDM；Fused Deposition Modeling)、层状物体制造(LDP；Digital Light Processing)、立体平版打印(SLA)及相关3D打印技术。
本发明具有以下技术优势：
(1)负温感水胶在温度上升时会有均压收缩的能力，让烧结粉 体能够致密化，其原理犹如粉末冷等静压(cold isostatic pressing；CIP)成型技术，可均匀收缩，减低收缩时内应力，故不需经缓慢耗时收干过程，可立即进行烧结过程，且易得到不龟裂的烧结体与较佳机械性质。
(2)负温感水胶的黏性可以经均匀搅拌气孔入泥状胚体，经烧结后可留下孔洞，也可真空搅拌除气以利3D打印，成为3D打印墨水材料，进行复杂形状与互穿性孔洞的基层打印产品。
(3)3D打印过程控制参数：a.机台的各种温度、压力、速度、打印孔径等等。b.陶瓷打印墨水材料粉粒大小、固液比、黏度、水胶浓度。c.打印槽基板需以液体油相来浸置，逐渐控制油高度可一方面来可控制打印材料的温度，二来可将水相泥状混合打印材料以油包覆，可更利后续高温收缩烧结过程，达成陶瓷烧节高致密化结果。
负温感水胶应用在3D打印上可添加光固化起始剂，使其可以通过UV光的照射进行固化成型，此项固化方式可以提高打印精细度及较复杂形状制作。
本发明提供一种积层制造3D打印物品的方法，包含：(a)以一3D打印机打印沉积一或多层浆体，其中所述浆体包含一陶瓷粉末的组合物；(b)进一步注入一油于所述一或多层浆体周围，其中注入的油的高度低于所述浆体的高度；(c)重复步骤(a)和(b)直到得到一具有所需几何形状的本体；及(d)藉由加热烧结所述本体以得到所述3D打印物品，其中所述3D打印机的打印载座温度为30至80℃。
在一较佳实施例中，所述浆体为一组合物，其包含陶瓷粉末、玻 璃粉末或金属粉末。在另一较佳实施例中，所述油包含但不限于合成油品(如聚二醇、硅油、氟化油、磷酸酯、聚醚等)、矿物油品(如石蜡、十二烷基醇等)、植物油(如橄榄油、大豆油等)、烃矿物油、液体石蜡或合成烃。在另一较佳实施例中，所述陶瓷粉末包含但不限于氢氧基磷灰石(HA)、磷酸三钙(TCP)、高密度氧化铝(Al2O3)、氧化锆(ZrO2)、生物活性玻璃(Biogiass；BG)、碳化物系陶瓷材料(如碳化硅(Silicon carbide)等)、氮化物系陶瓷材料(如氮化硅(Silicon nitride)等)、硅酸铝(aluminium silicate)、硼化物陶瓷材料或硅化物陶瓷材料。
在一较佳实施例中，所述浆体的黏度范围在100至900cP之间，所述3D打印机的喷嘴的大小范围在19至30G之间，而所述3D打印机的打印速度范围在0.1至5cm/s之间。
在一较佳实施例中，所述加热包含以下四个阶段：
第一阶段：在2小时内缓慢加热至600℃～650℃(3～6℃/min)，并维持所述温度30至60分钟；
第二阶段：在20～30分钟内快速将温度上升至1150℃至1250℃(15～25℃/min)，并维持所述温度10～30分钟；
第三阶段：在10～30分钟内缓慢加热至1250℃～1350℃(3～6℃/min)，并维持所述温度1至3小时；及
第四阶段：藉由冷却缓慢将温度降至25℃。
在一较佳实施例中，所述浆体由以下步骤制备：(a)合成聚(N-异丙基丙烯酰胺)(p(NiPAAm))或聚(N-异丙基丙烯酰胺-共聚-甲基 丙烯酸)(p(NiPAAm-MAA))；(b)将一分散剂与羟磷灰石混合；(c)将步骤(a)的所述p(NiPAAm)或所述p(NiPAAm-MAA)与水混合以得到一水凝胶溶液；(d)将步骤(c)的所述水凝胶溶液与步骤(b)的产物混合以产生一混合物；及(e)搅拌步骤(d)的所述混合物以产生所述浆体。在另一较佳实施例中，所述聚合物颗粒包含但不限于聚乙烯。
在另一较佳实施例中，步骤(b)的所述羟磷灰石与所述分散剂是以重量百分比范围25∶1至25∶5的比例混合。步骤(b)的所述分散剂可为聚丙烯酸(PAA)、聚甲基丙烯酸(PMA)或聚乙烯醇(PVA)及其类似物；步骤(b)的所述羟磷灰石或磷酸钙盐是在混合前在高温炉中烧结至700℃～900℃；步骤(c)的所述p(NiPAAm-MAA)与水是以体积比范围1∶10至2∶1的比例混合；步骤(e)的大分子颗粒具有与步骤(d)的混合物的总体积的5％～50％相等的体积。
在另一较佳实施例中，所述方法进一步添加一光固化起始剂于步骤(c)的水凝胶溶液，使所述浆体能够经UV照射而光固化成型。即负温感水胶UV光固化成型。所述光固化起始剂的种类包含游离基型光固化起始剂或阳离子型光固化起始剂。所述游离基型光固化起始剂包含但不限于丙烯酸或不饱和聚酯，所述阳离子型光固化起始剂包含但不限于环氧化合物、氧杂环丁烷或乙烯醚。
在一较佳实施例中，所述多孔陶瓷组合物具有纳米孔或微米孔，且可用作生物材料支架(biomaterial scaffold)；所述生物材料支架是部份生物可吸收的。在一较佳实施例中，所述生物材料支架被用作人 工骨，并与刺激骨生成的物质混合，其中所述刺激骨生成的物质选自由骨髓、BMP生长因子、血管生成因子、他汀类药物(statin drugs)、双膦酸盐药物、骨细胞、干细胞及其药物载体所组成的群组。在另一较佳实施例中，所述生物材料支架被用作治疗剂的载体。在一较佳实施例中，所述治疗剂为一抗生素药物。
本发明提供一具负温感性水胶混合陶瓷粉末系统可进行3D打印陶瓷结构，其包含负温感性水胶使用，所述负温感性水胶可为例如：氮-异丙基丙烯酰胺聚合物(poly(N-isopropylacrylamide；PNIPAAM)、氮-异丙基丙烯酰胺-甲基丙烯酸共聚合物(poly(N-isopropylacrylamide-co-methacrylic acid；PNIPAAM-MAA)其类似温感化合物；所述生物陶瓷材料可为氢氧基磷灰石(HA)、磷酸三钙(TCP)、高密度氧化铝(Al2O3)、氧化锆(ZrO2)、生物活性玻璃(Biogiass；BG)及其类似生物陶瓷材料；所述3D打印生物陶瓷打印技术可为沉积成型(FDM；Fused Deposition Modeling)、层状物体制造(LDP；Digital Light Processing)、立体平版打印(SLA)及相关3D打印技术。
附图说明
图1为3D打印生物用水胶陶瓷材料条件参数。
图2为3D打印技术可有效控制生物陶瓷孔洞大小、间距、图案。
图3为均匀收缩与强化烧结密度的实施例。
图4为磷酸盐陶瓷有无含油收缩率比较。
图5为氧化锆陶瓷有无含油收缩率比较。
图6为3D打印具互穿性孔洞磷酸钙盐生物陶瓷复合性材料支架(scaffold)。
图7为UV光固化成型3D打印磷酸钙盐生物陶瓷复合性材料支架(scaffold)。
图8为UV光固化成型陶瓷磷酸盐陶瓷含油收缩率比较。
图9为不均匀收缩后的陶瓷裂纹的示意图示。(干燥太快造成样本因不均匀收缩导致弯曲或裂缝)。
图10为不含油膜干燥的干燥粉末收缩的示意图。加热过程中，生胚外围水胶会先收缩，但升温过程，其外围水分也会散失，导致外部颗粒不易再具有高度收缩致密化。内部粉末在后续升温过程易发生孔隙。
图11为含油膜干燥的干燥粉末收缩的示意图。加热过程中，生胚外围因为油膜包覆，整体水胶会利于收缩进行，水往外围排出，故易具有较高收缩率帮助烧结致密化。内部粉末在后续升温过程，其孔隙度因高温烧结扩散，会下降许多。
具体实施方式
以下实施例非用于限定而仅是本发明的各个态样与特征的代表。
本发明是关于3D打印技术成型(积层制造)制作生物陶瓷，即为生医陶瓷(Bioceramics)。关于温感水胶制备含多孔性陶瓷组合物的方法可参考美国专利US8940203。本发明利用温感性水胶及3D打印技术结合制备多孔性陶瓷。因此本发明目标有(1)调整负温感性水胶/陶瓷粉末最佳3D打印成型条件范围的比例。(2)3D打印制作 过程中最佳控制条件范围。(3)3D打印制作生物陶瓷(HAp/β-TCP)/负温感性水胶(p(NiPAAm-MMA))，并检测分析。(4)3D打印制作含油(如硅油)生物陶瓷(HAp/β-TCP)/温感性水胶(p(NiPAAm-MMA))，并检测分析。(5)3D打印制作生物陶瓷(氧化锆，ZrO2)/负温感性水胶(p(NiPAAm-MMA))，并检测分析。(6)3D打印制作含油(如硅油)生物陶瓷(氧化锆，ZrO2)/负温感性水胶(p(NiPAAm-MMA))，并检测分析。(7)负温感水胶陶瓷添加UV光固化起始剂，进行光固化打印。其中负温感性水胶溶液与陶瓷粉墨混合搅拌比例，以负温感性水胶溶液的重量百分比浓度(wt％)及陶瓷粉末重量克重。3D打印负温感性水胶/生物陶瓷条件，以负温感性水胶温度敏感特性设计，调整打印载座上温度控制使其负温感性水胶相转变收缩，让陶瓷粉末间紧密，达成型效果。其他打印控制条件有打印头推挤出料器压、打印速度、打印出料端针头口径大小。3D打印制作生物陶瓷成型后以有无添加油品(验证中以硅油为范例)覆盖陶瓷进行高温烧结动作作为对照组别，检测其烧结前后及有无添加油品覆盖的收缩大小比例进行比较。在以两种不同的陶瓷粉末验证负温感性水胶系统及3D打印技术结合适用于不同陶瓷粉末。初步结果显示，负温感性水胶与生物陶瓷混合搅拌后其胶体黏度需达约100～900cP符合3D打印机台气体推动出料的50～200,000mPa.s范围。依照生物陶瓷粉末的颗粒大小及打印线条粗细，其适用选择打印针头的大小范围19～30G进行制作。3D打印制作打印头移动速度决定线条粗细因素之一，经实际测试最佳打印速度范围0.1～5(cm/s)为最 佳。比较3D打印制作有无含油类(硅油、碳氢矿物油、液体石蜡、石蜡、合成烃等等)生物陶瓷(HAp/β-TCP)/负温感性水胶(p(NiPAAm-MMA)或p(NiPAAm))烧结前后收缩率，其中以含油覆盖组具较高收缩比例，最高达27.9％的收缩率。比较不同生物陶瓷粉末比较，3D打印制作有无含油生物陶瓷(氧化锆，ZrO2)/负温感性水胶(p(NiPAAm-MMA))，烧结前后收缩率，同样含油覆盖组具较高收缩比例，最高达36％的收缩率。目前将烧结后陶瓷以扫描式电子显微镜(SEM)观察，可由正面观察到孔洞大小约500μm大小，再由侧面观察其表面型态，可看见由3D打印成型特有条状交错的堆栈型态。本发明成功制备一适用于3D打印生物陶瓷的系统，此系统负温感性水胶可与多项生物陶瓷材料很合使用，并由3D打印设备以温控方式打印多元型态，其中负温感性水胶与油相溶液结合使用进一步提升生物陶瓷收缩的效果。
1、负温感性水胶溶液与陶瓷粉末混合搅拌比例，以负温感性水胶溶液的重量百分比浓度(wt％)及陶瓷粉末重量克重，最佳实例会依陶瓷粉末的特性差异进行调整。以下为实际实施比例：
(1)磷酸钙(β-TCP)陶瓷粉末为1mL 15％的负温感水胶溶液添加2.0g磷酸钙陶瓷粉末真空搅拌混合8分钟，得可打印的浆体。
(2)氧化锆(ZrO2)陶瓷粉末为1mL 10％的负温感水胶溶液添加1.8g氧化锆陶瓷粉真空搅拌混合8分钟，得可以打印的浆体。
(3)氢氧基磷灰石(HAp)陶瓷粉末为1mL 15％的负温感水胶溶液添加2.0g氢氧基磷灰石陶瓷粉末真空搅拌混合8分钟，得可打 印的浆体。
2、3D打印负温感性水胶/生物陶瓷条件，以负温感性水胶温度敏感特性设计，调整打印载座上温度控制使其负温感性水胶相转变收缩，让陶瓷粉末间紧密，达成型效果。其他打印控制条件有打印头推挤出料器压、打印速度、打印出料端针头口径大小。
(1)3D打印制作打印头移动速度决定线条粗细因素之一，经实际测试最佳打印速度范围0.1～5(cm/s)为最佳。
(2)3D打印制作打印头出料速度决定线条粗细因素之一，经实际测试最佳初料速度23G针头(内径25mm)为主，气动推送出料所需气压为±4.5bar。
(3)3D打印制作负温感水胶固化成型条件，通过载座提升温度使得负温感性水胶相转化收缩，其温度±40℃。在另一较佳实施例中，打印载座的温度加温至30至80℃。
3、3D打印负温感性水胶/生物陶瓷制作，将打印完成后进行烧结动作前，以油品包覆打印完成的陶瓷，而后送入高温炉中烧结。以下为有无油品包覆收缩差异及陶瓷烧结温度：
(1)将上述搅拌混合的氢氧基磷灰石浆体，进行打印成形，打印直径约14mm*高3mm的对象，分别其中之一以硅油包覆，送至高温炉中以±1250℃的梯度温度进行烧结6～8小时。完成后进行直径与高度测量，得其收缩率(如图4)，未添加硅油的陶瓷块烧结后收缩比例：直径10％、高11.0％；硅油滴附的陶瓷块烧结后收缩比例：直径27.9％、高21.3％。
(2)将上述搅拌混合的氧化锆浆体，进行打印成形，打印直径约18.10mm的对象，分别其中之一以硅油包覆，送至高温炉中以±1400℃的梯度温度进行烧结6～8小时。完成后进行直径与高度测量，得其收缩率(如图5)，未添加硅油的陶瓷块烧结后收缩比例：直径23.4％；硅油滴附的陶瓷块烧结后收缩比例：直径36.08％。
4、负温感性水胶/生物陶瓷3D打印成型技术：
先前固化技术使用温度控制进行打印制作，但是负温感水胶具有光固化机制的官能基结构，可以通过添加光固化起始剂，即可转换为光固化成形方式进行打印。
光固化打印实施案例，将15％负温感水胶添加1～5％光固化起始剂I2959(UV吸收波长为365mm)搅拌1～2天，而后与氢氧基磷灰石(HAp)陶瓷粉末搅拌，以1mL 15％的负温感水胶溶液添加2.0g氢氧基磷灰石陶瓷粉末真空搅拌混合8分钟，得可打印的浆体。进行打印时通过UV模块的设定给与光固化的路径及相关照射时间使得固化成形(如图7)，打印一直径15mm*高5mm的陶瓷并滴附硅油包覆，送至高温炉中以±1250℃的梯度温度进行烧结6～8小时。完成后进行直径与高度测量，得烧结后尺寸，直径为11.26mm、高3.88mm的陶瓷块，其收缩比率分别为直径25％、高22.4％。(如图8)
结果：
上述实验结果中可确认：
(1)本发明所使用的负温感水胶混合搅拌陶瓷粉进行3D打印成型的技术为可行的3D成形技术。
(2)3D打印成型过程，打印的参数可调整，浆体出料速率、打印头移动速率、载台温度、打印针头的内径等，相关的参数控制进行制作。
(3)负温感水胶系统可与多数陶瓷粉末一起混合搅拌，进行制作烧结，可通过负温感水胶相转化收缩的特性，固化成形进行打印，并再烧结过程中温度提高进而加大收缩力，类似传统陶瓷工艺上类均压的工法，如同上述实验结果所示，可达10～20％的收缩率。
(4)本发明实验中提出通过油品的滴附在打印完成的陶瓷对象进行包覆的动作，此项步骤可有效提升陶瓷烧结时收缩的效果，如同上述实验结果所示，可达20～40％的收缩率，较未滴附油品的陶瓷具有较大的收缩率。
(5)本发明所用负温感水胶材料可添加光固化起始剂，使之转化为具有光固化能力胶体材料，在打印上可通过UV光的照射达到固化效果，且收缩的能力不变。

Claims (15)

  1. 一种积层制造3D打印物品的方法，包含：
    (a)以一3D打印机打印沉积一或多层浆体，其中所述浆体包含一陶瓷粉末的组合物；
    (b)进一步注入一油于所述一或多层浆体周围，其中注入的油的高度低于所述浆体的高度；
    (c)重复步骤(a)和(b)直到得到一具有所需几何形状的本体；及
    (d)藉由加热烧结所述本体以得到所述3D打印物品，其中所述3D打印机的打印载座温度为30至80℃。
  2. 如权利要求1所述的方法，其中所述浆体为一组合物，其包含陶瓷粉末、玻璃粉末或金属粉末。
  3. 如权利要求2所述的方法，所述陶瓷粉末包含氢氧基磷灰石、磷酸三钙、高密度氧化铝、氧化锆、生物活性玻璃、碳化物系陶瓷材料、氮化物系陶瓷材料、硅酸铝、硼化物陶瓷材料或硅化物陶瓷材料。
  4. 如权利要求1所述的方法，其中所述油包含聚二醇、硅油、氟化油、磷酸酯、聚醚、石蜡、十二烷基醇、橄榄油、大豆油、烃矿物油、液体石蜡或合成烃。
  5. 如权利要求1所述的方法，其中所述浆体的黏度范围在100至900cP之间。
  6. 如权利要求1所述的方法，其中所述3D打印机的喷嘴的大小范围在19至30G之间。
  7. 如权利要求1所述的方法，其中所述3D打印机的打印速度范围在0.1至5cm/s之间。
  8. 如权利要求1所述的方法，其中所述浆体由以下步骤制备：
    (a)合成聚(N-异丙基丙烯酰胺)(p(NiPAAm))或聚(N-异丙基丙烯酰胺-共聚-甲基丙烯酸)(p(NiPAAm-MAA))；
    (b)将一分散剂与羟磷灰石混合；
    (c)将步骤(a)的所述p(NiPAAm)或所述p(NiPAAm-MAA)与水混合以得到一水凝胶溶液；
    (d)将步骤(c)的所述水凝胶溶液与步骤(b)的产物混合以产生一混合物；及
    (e)搅拌步骤(d)的所述混合物以产生所述浆体。
  9. 如权利要求8所述的方法，其进一步包含在步骤(e)之前将聚合物颗粒加入步骤(d)的所述混合物。
  10. 如权利要求8所述的方法，其中步骤(b)的所述羟磷灰石与所述分散剂是以重量百分比范围25：1至25：5的比例混合。
  11. 如权利要求8所述的方法，其中步骤(b)的所述分散剂为聚丙烯酸(PAA)、聚甲基丙烯酸(PMA)或聚乙烯醇(PVA)。
  12. 如权利要求8所述的方法，其中步骤(c)的所述p(NiPAAm-MAA)与水是以体积比范围1：10至2：1的比例混合。
  13. 如权利要求8所述的方法，其进一步添加一光固化起始剂于步骤(c)的水凝胶溶液，使所述浆体能够经UV照射而光固化成型。
  14. 如权利要求13所述的方法，其中所述光固化起始剂为游离基型光固化起始剂或阳离子型光固化起始剂。
  15. 如权利要求14所述的方法，其中所述游离基型光固化起始剂包 含丙烯酸或不饱和聚酯，所述阳离子型光固化起始剂包含环氧化合物、氧杂环丁烷或乙烯醚。
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